Chemically modified amino and ammonium functional hydroxy polymers, especially carbohydrates, are widely used in industrial applications from building materials and paper production to pharmaceuticals and cosmetics. Starch is one of the most important natural hydroxy polymers. It is a renewable and feasible raw material and the third most used component by weight in paper industry, where the main role of starch is to improve the strength of the paper. Starch is also used as an adhesive in surface sizing and as a binder in coating formulations. The bonding of starch to cellulosic fibres is generally improved by addition of cationic substituents to the starch backbone. The positively charged cationic starch, containing amino or ammonium groups, has a strong affinity for negatively charged surfaces and particles i.e. cellulosic fibres and mineral pigments.
Cationic starches are also used in textile industry to improve the textile feel of the fabric. In U.S. Pat. No. 5,447,643 an aqueous fabric softener is stabilised by addition of cationic starch or chitosan.
In waste water treatment, the use of cationic starches improves the retention of anionic impurities in the flocculation processes. For instance, patent publication WO 2004/041732 introduces the use of cationic starch and a brine solution in the treatment of water and wastewater.
Cationic hydroxy polymers have also a strong affinity for keratinous matter and therefore cationized guar gum and starch are widely used in hair and skin care products. The use of low molecular weight cationic starches in cosmetics and the treatment of a keratin-containing substrate is disclosed in U.S. Pat. No. 6,365,140. Another cosmetic treatment composition comprising cationic starch betainate has been described in patent publication WO 02/07684, which also covers a cosmetic treatment method for keratinous matter and use for washing skin.
Several methods have been developed for the cationization of starch and other hydroxy polymers. The cationization is generally carried out by etherification of starch with 2,3-epoxypropyl trimethylammonium chloride or 3-chloro-2-hydroxypropyl trimethylammonium chloride in an alkaline aqueous slurry or a dry process. The common cationization reagent can give undesirable reaction by-products.
The generally known methods for preparing carboxylic acid esters of starch involve the use of acid chlorides or anhydrides in organic solvents such as pyridine or 1,4-dioxane. Patent publication WO 00/15669 illustrates the esterification of starch using acid chloride of betaine in 1,4-dioxane and pyridine. Patent FR 2805270 concerns novel types of cationic polymers and polymeric matrices, degradable in the organism, and with controlled rate of degradation, useful as such or as vehicles for different compounds, in particular molecules with biological activity. FR 2805270 also describes a method for producing said polymers and matrices from maltodextrins and acid chlorides of betaines in pyridine and DMF.
The use of undesired and relatively expensive solvents and reagents generate both environmental load and high price for starch esters and may leave traces of harmful substances in final products. Therefore, the general esterification methods do not fulfil the requirements for the large-volume and low-cost starch esters, especially when the application of the starch ester may be involved in food products, cosmetics or pharmaceuticals.
A method for the preparation of phosphate esters of starch by heating dry mixtures of starch and inorganic salts of phosphoric acid is generally known. The common manufacturing procedures are exemplified by U.S. Pat. No. 2,884,412 and U.S. Pat. No. 2,865,762. These procedures involve impregnating starch granules with alkali metal phosphates or other phosphate reagents in aqueous slurries, drying of the starch granules without gelatinizing them to a moisture content of less than 20%, and then heating of the dry granules to reaction temperatures of about 120 to 175° C. A similar dry phosphorylation process is described in U.S. Pat. No. 6,365,002, where amphoteric starch additives for papermaking are produced by phosphorylation of cationic starch. The amphoteric starch phosphates provide advantageous paper properties and improved wet end performance.
An analogous method for the preparation of highly crosslinked and water insoluble starch esters of citric acid has been published in Starch/Stärke 48 (1996) 275-279. In the esterification procedure, dry mixtures of starch and sodium salts of citric acid are heated at 110-140° C. for 2-24 h. The thus prepared water-insoluble starch citrates were used as biodegradable ion-exchangers for metal ions.
In the patent publication DE 4208946, water insoluble starch acetates containing amino acid esters are prepared for the manufacture of biodegradable plastics. However, the procedure involves the use of acid anhydrides, and produces amino acid esters in N-acylated form. The N-acylation of amino acids is usually an undesired reaction and reduces the functionality of amino acid esters of starch in applications where the presence of free amino groups is required.
The production of anthranilic acid ester of starch and its use as a paper retention aid has been described in the patents NL 6717509, U.S. Pat. No. 3,499,886, U.S. Pat. No. 3,511,830, U.S. Pat. No. 3,513,156 and U.S. Pat. No. 3,620,913. The esterification of starch is performed using isatoic anhydride in an organic solvent or an aqueous slurry. Isatoic anhydride (i.e. N-carboxy anhydride of anthranilic acid) is generally prepared from anthranilic acid and phosgene. The hydrolysis product shows biological activity.
A retention aid for chemical pulp prepared by derivatization of dialdehyde starch with betaine hydrazide has been described in Tappi 44 (1962) 750. However, the thus formed hydrazones of starch are harmful and their preparation is complex and unfeasible.
U.S. Pat. No. 2,170,272 describes the thinning of starch pastes for textile and paper sizing purposes by heating starch pastes in the presence of acid salts of amino acids, such as betaine hydrochloride. The thinning process is carried out for starch pastes containing over 90% of water at temperatures around 85° C. and therefore, no esterification of amino acids is involved. The purpose of amino acids in the patented process is to immobilise strong acids, which are responsible for the thinning (i.e. acid hydrolysis) of starch, so that dry blends of acid salts and starch can be safely stored prior to the thinning by cooking.
Patent publication WO 2004/104049 covers a method for the preparation of carnitine esters of starch and other hydroxy polymers, and their use in several fields of industry, for example as an additive in the manufacture of paper. The esterification of a hydroxy polymer, preferably starch, with β-lactone of carnitine is most feasibly carried out in an aqueous slurry. The carnitine esters of starch are considered as more physiologically acceptable and biodegradable than traditional cationic starch ethers.
Patent publication US 2003/0027733 describes the preparation of nitrogenous carboxylic esters of cellulose to be used as antibacterial agents with flame retardant properties. The invented process consists of a heat-treatment of cellulose in the presence of certain amino acid esters. However, the process has a very poor reaction efficiency of 1-10% and the harsh and highly acidic reaction conditions exploiting hydrochlorides of amino acids are not suitable for more sensitive hydroxy polymers i.e. starch.
Patent publication WO 2004/104048 describes a solventless esterification process of starch and other hydroxy polymers, where the homogenous mixtures of a hydroxy polymer, a free amino, alkylamino or quaternary ammonium acid and an acidulating agent are heated to yield hydroxy polymer esters containing amino, alkylamino or quaternary ammonium groups. The invented process simultaneously hydrolyses the polymer structure during the esterification in acidic conditions, which may restrict the available molecular weight range of the products.
Patent publication WO 00/50493 concerns a method for making a cellulose or starch fatty ester by esterification or trans esterification of a cellulosic or starchy material using a fatty reagent. The process is performed in solid or fragmented state in a double screw extruder at a temperature ranging between 180° C. and 230° C. The invented method claims to make cellulosic or starchy material hydrophobic without using toxic solvents.
The new process improves the former dry esterification process described in the patent publication WO 2004/104048 by introducing the use of esters of amino, alkylamino and quaternary ammonium acids, preferably methyl betainate chloride and methyl carnitate chloride as esterifying agents. The new alkaline trans esterification process allows far greater reaction efficiencies (RE) and much better preservation of high molecular weights of hydroxypolymer than the former acidic dry esterification process of nitrogenous carboxylic acids. Hereby, the use of alkalising agent, such as ammonia, to promote solid state trans esterification allows the production amino or quaternary ammonium functional hydroxy polymer esters with a reasonable yield and only negligible decrease in the molecular weight.